O-(benzyl or benzoyl)-benzoic acid-azo-phenyl compounds

ABSTRACT

Polyester is dyed through thermofixation in fast shades with azo dyestuffs of the formula   WHEREIN R1 is hydrogen, chlorine, bromine, lower alkyl, or lower alkoxy; R2 is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R7CONH- or R7SO2NH-; R3 is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl) or   R4 is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or   ONE OF R5 and R6 is hydrogen or methyl; AND THE OTHER R5 and R6 is hydrogen; EACH R7 is independently lower alkyl, chloro(lower alkyl) bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, lower alkoxyphenyl or cyanophenyl; X is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy(lower alkyl) or lower alkoxy(lower alkoxy); Y is hydrogen, chlorine, or bromine; and Z is methylene or carbonyl.

United States Patent [1 1 Renfrew et al.

[451 May 20, 1975 O-(BENZYL OR BENZOYL)-BENZOIC ACID-AZO-PHENYL COMPOUNDS [75] Inventors: Edgar Earl Renfrew; Dominic Andrew Zanella, both of Lock Haven, Pa.

[73] Assignee: American Aniline Products,

Incorporated, Paterson, NJ.

[22] Filed: Apr. 6, 1972 [21] Appl. No.: 241,810

[52] U.S. Cl. 260/207; 260/207.1; 260/517; 260/518 R; 260/518 A; 260/519; 8/41 C [51] Int. Cl.... C09b 29/08; C09b 29/26; D06p 1/06 [58] Field of Search 260/207, 207.1

[56] References Cited UNITED STATES PATENTS 2,317,365 4/1943 Dickey et a1 260/207 X 3,359,256 12/1967 Mueller et al. 260/207.1 X 3,398,136 8/1968 Groebke et a1. 260/207.l X 3,417,076 12/1968 Sartori 3,552,905 l/l97l Sartori 260/207.l X

FOREIGN PATENTS OR APPLICATIONS 419,670 11/1934 United Kingdom 260/198 262,243 12/1926 United Kingdom 260/207 Primary ExaminerFloyd D. I-Iigel Assistant Examiner-C. F. Warren Attorney, Agent, or Firm-Armstrong, Nikaido& Wegner [57] ABSTRACT Polyester is dyed through thermofixation in fast shades with azo dyestuffs of the formula wherein R is hydrogen, chlorine, bromine, lower alkyl, or

lower alkoxy; R is hydrogen, chlorine, bromine, lower alkyl,

lower alkoxy, R CONI-I- or R SO NH; R is hydrogen, lower alkyl, hydroxy(lower alkyl),

lower alkoxy(lower alkyl), cyano(lower alkyl),

chloro(lower alkyl), bromo(lower alkyl) or R is hydrogen, lower alkyl, hydroxy(lower' alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or 5 Claims, No Drawings O-(BENZYL OR BENZOYL)-BENZOIC ACID-AZO-PHENYL COMPOUNDS BACKGROUND OF THE INVENTION A20 dyes bearing water solubilizing groups have long been known as dyestuffs for natural polyamide fibers. Typically such azo dyes have contained at least one sulfonic acid group, although a relatively minor amount of the research in azo dyes for natural polyamide fibers has been devoted to sulfonic acid-free azo dyes which contain at least one carboxylic acid group. It is generally recognized in the art that such azo dyes are generally unsuited for the dyeing of synthetic fibers such as polyethylene terephthalate.

We have now discovered a novel dyeing process which makes use of the thermofixation process and a specific class of azo dyes which yields excellent dyeings on polyesters, particularly polyethylene terephthalate, with azo dyes containing a free carboxylic acid group.

SUMMARY OF THE INVENTION In accordance with the invention there are provided polyester dyeings with compounds of the formula:

2 @cooa Y wherein R, is hydrogen, chlorine, bromine, lower alkyl, or

lower alkoxy,

R is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R CONH or R SO NH;

R is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxy(lower alkyl), cyano(lower alkyl), chloro (lower alkyl), bromo(lower alkyl) or -CHCHOICR I I II R, is hydrogen, lower alkyl, hydroxy(lower alkyl), lower alkoxyflower alkyl), cyano(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, chlorobenzyl, bromobenzyl, nitrobenzyl or 43110 HOCR; I I II 7 R- R Z is methylene or carbonyl.

DETAILED DESCRIPTION As the starting material for the preparation of the azo dyestuffs(l) may be mentioned a base of the formula z I O0 00H 1 I Y l wherein X, Y and Z are as defined above. The base (II) is converted to a diazotized base of the formula (III) OOH wherein X, Y and Z are as defined above and An is anion. To produce the azo dyestuffs (I), the diazotized 30 base (III) is treated with acoupler of the formula R 3 (IV) wherein R R R and R are as defined above.

A convenient diazotization method involves treating the base (II) in cold water containing enough hydrochloric acid to make the medium strongly acidic and adding thereto an amount of sodium nitrite at least stoichiometrically equivalent to the amount of base, the reaction mass being maintained at or near the temperathe coupler. A buffering agent, such as sodium acetate may be added to reduce the acidity to a pH of 5 to 7. The mixture is allowed to react for up to several hours at room temperature and is thereafter filtered and washed acid free. The desired azo dyestuff (I) is thus obtained in the form of a wet cake.

It may be noted that in the particular cases where R and R are together desired to be hydrogen, it is often advantageous to convert the coupler (IV) to the arylaminomethanesulfonic acid salt (V) through the use of formaldehyde and sodium bisulfite in known manner.

ture of melting ice. A surface active material with the diazonium salt to a cold aqueous acidic solution of NHCH SO Na (V) Coupling may then be carried out the usual After formation of the monoazo body, hydrolysis of the soluble in dilute aqueous alkali due to the carboxylic group. Neutralization of the hydrolysis medium facilitates isolation of the azo dyestuff (1)). The method is especially useful in those cases in which R is hydrogen, alkyl, chlorine or bromine, and often helpful in achieving better yields when R is alkoxyl.

The products produced from the coupling reaction, when suitably dispersed, are excellent dyes for polyester fabrics, and are particularly suited for dyeing polyester by thermofixation methods.

To prepare the product for application to the polyester substrates the product must be suitably dispersed. This may be done in any of several well-known methods, milling as in a ball-mill with dispersing agents such as lignin sulfonic acid materials, for instance. The resultant aqueous dispersion can be dried, as in a spraydrye r, or preserved and used as a paste. Standardizationto any desired lower strength can be done with inert colorless diluents such as inorganic salts for powders, or water for pastes. Other materials such as preservatlves, foam-control agents, and wetting agents may be added as desired.

Dispersed pastes are made by wet milling the dye in conventional equipment in the presence of a dispersing agent, preferably sodium lignin sulfonate or sodium alkylnaphthalene sulfonate. Various other commercially available dispersing agents, such as sodium salts of carboxylated polyelectrolytes and the naphthalene sulfonates; e.g., the condensation products of sulfonated naphthalene and formaldehyde, such as soidum dinaphthylmethane disulfonate, are conveniently used. The oil disperse paste may be cut or standardized to a standard strength with water. The final color content of the finished paste averages from -40 percent by weight (pure color) active dye base.

Disperse powders are prepared by wet milling color in the presence of a dispersant, such as those mentioned hereabove, in equipment such as a ball-mill, Werner-Pfleiderer mill or attritor. The dispersed material is oven or spray dried and micropulverized if necessary to provide the dispersed powder. The color is cut or standardized to a standard strength in a blender with a diluent, such as sodium sulfate ordextrin. A wetting agent, such as sodium cetyl sulfate or an alkylphenoxy polyethanol may be added to aid in wetting out the product when it is placed in the dye bath. Disperse powders are usually cut or standardized to 2560 percent by weight color content (pure color).

The dye is preferably applied to the aromatic polyester fiber by thermofixation methods, such as the Thermosol" process. This process involves padding the cloth with a dilute dye dispersion, followed by drying to remove water (e.g., by preheating -with infrared heat) and curing by dry heat fixation using dried hot air or heated contact rolls. Curing or fixation temperatures 4 of 350-430F are used for less than 2 minutes, usually for 30 to 90 seconds. Ordinarily, if'the padded fabric is entirely polyester, curing is done at 400430F. If the fabric contains cotton or viscose rayon, apart from synthetic fibers, there is little danger of damaging cellulosic portions, but if wool is present, the curing temperature must bekept below 357F and the time must be reduced to about 30 seconds.

i For durable press finishing of mixed polyester-cotton blends, after thermofixation the residual unfixed dye is removed from the fabric by scouring and the cleaned fabric is given a durable press cure at 300-3 50F. The

i new dyes of the invention show an excellent diffusion rate in, the polyester fibers at the dyeing temperature and a low diffusion rate at the preferred press curing temperature of 300-350F.

In order to evaluate the effectiveness of a particular dye for a given type of fiber, the dyed fiber is examined for substantivity of the color, light fastness of the color. and resistance of the color to sublimation. Specific tests for the evaluation of these important properties are described in the examples that follow.

The invention is further illustrated by the following examples:

EXAMPLEI [T cs 4 I coon M.W. 407.5

A. Diazo There is charged to a 3000 ml. beaker 300.0 ml. water 7 60.0 g. hydrochloric acid (32 percent) 55. l 1 g.4-chloro-3'-amino-o-benzoylbenzoic acid (0.2 mole) and 5.0 g.Tween 20 (a commercially available surface active material). 7

The mixture is heated to C, allowed to stir and cool to 30C and iced to 0C. At 05C there is added to the mixture, during a period of 15 minutes, a solution of a 15.0 g. sodium nitrite dissolved in 50.0 ml. cold water.

The diazotization mixture is stirred 2 hours at 05C, then the excess nitrous acid is destroyed with sulfamic acid and the diazo clarified and kept at 05C.

B. Coupler A 4000 ml. beaker is charged with 400.0 ml. water at 60C 25.0 g. N,N-dimethylaniline (0.206 mole) and 30.0 g. hydrochloric acid (32 percent).

The mixture is stirred to complete solution and iced to 0C.

C. Coupling The diazo solution is added to the coupler solution at 05C. The mixture is stirred 16 hours, during which time the temperature is allowed to rise to that of the room. The solids are then isolated by filtration and the filter cake iswashed acid free and dried.

Yield: 77.0 g.;95.5 percent 0.2'mo1e 81.5 g.) DuDispersion I r i I A'laboratory ball-mill is charged with 60.0 g. dry color (A', above) 58.0 g. Lignosol FTA" (a commercially available ligninsulfonic acid dispersing agent). and

282.0 ml. cold water.

' Dyeings' of clear red hues are obtained by treating polyethylene terephthalate fabric in known manners The mixture is ball-milled i'or 12 hours. A'paste of 15 I percent color content was obtained.

Dispersion: adequate, as shown by filter tests.

E. Evaluation 1 When appliedto polyethylene terephth alate bythe recognized method (carrier, pressure, thermofixation) golden yellow hues of excellent light fa'stness and sublimation fastness are obtained. The dye is especially suit- 1 able for thermofixation dyeing.

EXAMPLE Ii /CH2CH2CE(XH3 I I cn ca oc ocu CO NHCGIH3 1 A. Diazo There is charged to a 3000 ml. beaker 3000 ml. water 60.0 g. hydrochloric acid 32 percent) 55.1 g. 4-chloro-3"-amino-o-benzoylbenzoic acid then the excess nitrous acid is destroyed with sulfamic acid and the diazo clarified and kept at O-5C. B. Coupler A 4000 ml. beaker is charged with 200.0 g. ice, '1 200.0 ml. water, 67.6 g. 2,2'(3-acetamidophenylimino)diethanol acetate (0.21 mole), 40.0 g. hydrochloric acid (32 percent) and 50.0 g. acetic acid. The mixture is stirred to solution and iced to 0C.

C. Coupling Coupling is carried out in the way described in Example 1, Part C. A Yield: 111.0 g. 91 percent (0.2 mole 121.6 g.)

D. Dispersion I A laboratory ball-mill is charged with 60.0 g. monoazo material, (part C, above) 58.0 g. Lignosol PTA and 282.0 ml. cold water. 1

The mixture is milled for 12 hours. A disperse paste containing 15 percent of dye base is obtained. The dispersion is satisfactory as shown by filter tests.

E. Evaluation C. Coupling with' the dispersion fro'm'D above.'The dye dispersion is especially well suited for thermofix dyeing. Resistance to sublimation is outstandingly good.

1 EXAMPLE 111 p cooii A. Diaz o I v There is charged 350.0 ml. water 60.0 g. hydrochloric acid (32 percent) 54.2 g.4 methoxy,-3'-amino-o benzoy'lbenzoic acid I (0.2 mole)and 4.0 g.Tween 20." i

The mixture is heated to 70C, allowed to stir and cool to 30C and iced to 0C. At 05C there is added to the mixture, during a period of 15 minutes, a solution of .15.0 g. sodium nitrite dissolved in 50.0 ml. cold water. I I The diazo tization mixture is stirred 3 hours at 0-5C.

to .1 3000 ml. beaker Then the excess nitrous acid is destroyed with sulfamic acid and the diazo clarified and kept at 0-5C. B. Coupler A 4000 ml. beaker is charged with 400.0 ml. water at C v 25.0 g. N,N-dimethylaniline (0.206 mole) and 30.0 g. 32 percent hydrochloric acid.

The mixture is stirred to complete solution and iced to 0C.

The coupling of the materials from Part A and Part B is carried out in the manner described in Example I,

Part C.

Yield: 71.--g. 88 percent (0.2 mole 80.6 g.) D. Dispersion A 15 percent color content disperse paste is made in the manner described in Example I, Part D. E. Evaluation Dyeings on polyethylene terephthalate fabric produced by the disperse paste, Part D above, in established ways show clear scarlet dyeings of good proper- EXAMPLE IV A diazonium solution is prepared exactly in the manner of Example I, Part A. B. Coupler I A'coupler solution is prepared exactly in the way described in Example I, Part B, except that 30.6 g. N,N- diethylaniline (M.W. 149; 0.205 mole) is used instead of N,N-dimethylaniline. C. Coupling The diazonium salt and the coupler are combined exactly in the way described in Example I, Part C. and the product isolated and treated similarly. The dry weight of the monoazo body produced is 84.5 g, or 97 percent of the theoretical yield of 87.0 g. D. Dispersion A 15 percent disperse paste is prepared in the way described in Example I, Part D.

E. Evaluation Dyeings of the disperse paste (Part D, above) on polyethylene terephthalate fabric show a clear yellowish orange hue. Properties are very like those of the product of Example l, being excellent in fastness to light and to sublimation. The dye gives excellent color yield when dyed by the thermofixation method.

EXAMPLES V-LVll By substituting an equimolar' amount of the base (II) for the 3'-amino-4'-chloro-o-benzoylbenzoic acid and an equimolar amount of coupler (IV) for the N,N- dimethylaniline of Example I, otherwise following the procedure of Example l, 2120 dyestuffs (l) which dye polyethylene terephthalate via thermofixation in the shade indicated are obtained.-

7 Hue on EXAMPLE x Y 2 R1 R2 R3 I R4 Polyethylere Terephthale te v c1 H c= H H CH2CH20HH l CHZCHZOH Orange v1 01 H c=o H H 0 H CHZCHZCN Orange Reddist v11 (:1 H 011 H H v CH3 CH3 yellow VIII ocH H CH2 H H CHZCHZCN ca c cu scarlet IX Br vH C=O H H CHZCHZCN H orange X 01 C= H NHCCXIH3 C2115 Gil-l scarlet XI C1. H C= CH3 H CHZCHZOH CHZCHZOH orange x11 H H c= OCH 0H CH 0H 0H cH 0H 0H reddish 3 3 2 2 2 2 orange XI'II" H H c=o ocH OCH 0 0 OH cH CH CH dull I 3 3 2 2 2 2 red XIV c1 H c= 0C2H5 NHCOCH3\ Cil Cl-l 0C0CH cH cH ococH bordeaux xv 01 H c=o OCH3 NHC0Cll cH c r coc H cH cH ococ bordeaLx xv1 01 H CH2 OC2H5 NHcocH cH cH cN C2H5 rublne XVI]: C1 H C=O (X12115 mall-l CHZCHZWWHZCI H mO I bordea xvur CH3H c=o H H CH3 cH orange l dull XIX (1 H H 0-0 H NHCO-Q cn cn ococu CH2CH2CCOCH3 xx 01 H c=o 0on CH3- cH cH Br CHZCHZCN red xx: Y H H c= can our H H yell Sh 3 3 t red (XXII 01 H c =o H nuso gcn cii ou cH cH o red XXIII 01 H c=o 00H H H H yell sh orange XXIV H C=0 H C1 CZH5 02H5 orange xxv 01 H c=o ocH HHso cH cH cH ocoBr cH c ococ H plum HUE ON El POLYETHYL NE EXAMPLE x Y 2 4 TEREPHTHAIATE L OCH3 H C O H NHCQCN CH2CH?OCOCH3 CHZCHZOCOCH3 siglsh LI Cl H C= OCH3 NHCOQ'CIZH CH CH (XI L bordeaLx CH CH (XICXIH L11 01 H c=0 ocH CH3 CH CH OC0tEH C2115 red LIII Cl H C=O H H CZH5 CH2 orange LIV C1 H C=O H H CH3 CH2-{/ orange LV 01 H c=o H H (3 H CH c1 orange LVI H H c=0 H CH (1 1-1 CH scarlet LVII Cl H C=O H H CHZCHZCN CH2 Br orange What is claimed is: phenyl, lower alkoxyphenyl or cyanophenyl; 1. A compound of the formula X is hydrogen, chlorine, bromine, lower alkyl, lower R1 alkoxy, hydroxy(lower alkyl) or lower alkoxy(- 3 lower alkoxy); and 1 Y is hydrogen, chlorine, or bromine.

R 2. A compound of the formula 4 R E45 2 f 1 3 COOH N N- N wherein R is hydrogen, chlorine, bromine, lower alkyl, or COOH lower alkoxy; R is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R CONH or R SO NH-; R3 is hydrogen lower alkyl, hydroxyuower alkyl), R 18 hydrogen, chlorine, bromine, lower alkyl, or

lower alkoxy(lower alkyl), cyano(lower alkyl), Q alkoxy; chloro(lower alkyl), bromo(lower alkyl), or R is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, R CONl-l or R SO NH; R, is hydrogen, lower alkyl, hydroxy(lower alkyl),

0 C. 3 f a J lower alkoxy(lower alkyl), cyano(lower alkyl),

8 H. o chloro(lower alkyl), bromo(lower alkyl), or

H- LH""%'R73 l i R, is hydrogen, lower alkyl, hydroxy(lower alkyl), R; R. 9

lower alkoxy(lower alkyl), cyano(lower alkyl), ChIOYOUOWeT y bmmoflowef yl), nzyl, R4 is hydro en, lower alkyl, hydroxy(lower alkyl),

g chlorobenzyl, bromobenzyl, mtrobenzyl or lower alkoxy(lower alkyl), cyuno(lower alkyl), chloro(lower alkyl), bromo(lower alkyl), benzyl, H 0 a t chlorobenzyl, bromobenzyl, nitrobenzyl or l l n H-cH-0@% 7.\ s 6 a; 1 0

one of R and R is hydrogen or methyl; and the other of R and R,; is hydrogen:

each R is independently lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylone of R and R. is hydrogen or methyl; and the other of R and R is hydrogen;

each R is independently lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl),

3,884,901 13 14 phenyl, chlorophenyl, bromophenyl, lower alkyl- 4.Th dfl' 2fthf l' phenyl, lower alkoxyphenyl or cyanophenyl; e Comp-Dun o am 0 e ormu d X is hydrogen, chlorine, bromine, lower alkyl, lower l /CH2CH2OCOCH3 alkoxy, hydroxy(lower alkyl) or lower ulkoxy(- N N N lower alkoxy); and CH CH 0C0CH Y is hydrogen, chlorine, or bromine. NHCOCH 3. The compound of claim 2 of the formula:

' l COOH 6 H I 10 5. The compound of claim 2 of the formula 3 CH i I -N N N 001i J CH @C OOH 

1. A COMPOUND OF THE FORMULA
 2. A compound of the formula
 3. The compound of claim 2 of the formula:
 4. The compound of claim 2 of the formula
 5. The compound of claim 2 of the formula 